Detergent composition



Patented Oct. 24, 1950 DETERGENT COMPOSITION Walter C. Preston,Cincinnati, Ohio, asaignor to The Procter & Gamble Company, Cincinnati,Ohio, a corporation of Ohio No Drawing. Application February 24, 1947,Serial No. 730,558

The present invention relates to detergent compositions, and moreparticularly to soap-comtaining compositions which are highly resistantto curd-forming ingredientsof hard water.

It is well known that the use of ordinary toilet or household soap inhard water results in the formation and precipitation of insoluble fattyacid salts, more commonly referred to as lime soaps. It is also knownthat such precipitated lime soaps have a tendency to coagulate and forma sticky curd. This curd is commonly observed in the washstand and bathtub and also in the laundry rinse tub where it rises to the surface ofthe water as a scum, adheres to the walls of the tub as a ring, andsticks to the clothes during the rinsing operation, thereby giving tothe clothes an unsightly dingy appearance, producing spots uponsubsequent ironing, and often causing the development of a rancid odor.When soap is used for shampooing the hair, rinsing with hard waterresults in deposition of the lime soaps on the hair. In applications asdivergent as the dyeing of textile fabrics and the plating of metals,the formation of lime soaps has undesirable effects.

In face, whenever soap is used in hard water, insoluble lime soap curdforms during the rinsing process when the soap dilution becomessufficiently great to destroy the foaming and dispersing power of thesoap.

The coagulation of the lime soaps to form soap curd is dependent notonly on the degree of dilution of the soap in the hard water, but alsoon the age of the solution and on the degree of violence of agitation towhich it is subjected, increasing age and increasing agitation bothbeing important factors in promoting coagulation.

The primary object of the present invention is to provide a soapcomposition which forms little or no lime soap curd when used with hardwater.

Another object is to provide a detergent composition which will not forma sticky lime soap curd which 'will cling to clothes or form theunsightly, difficulty removable soap ring in the washstand or bathtub.

A further object is to increase the resistance of soap-containingdetergent compositions to precipitation of lime soap and the coagulationthereof to form curd when such compositions are used in hard water underconditions involving prolonged standing or agitation.

It is known that synthetic detergents such as the various organicsulfonates, alkyl sulfates, and other organic sulfuric acid derivatives,when mixed or used with soap in hard water are capable of 5 reducing theformation of lime soap curd. Sev- 14 Claims. (01.252-121) I erai suchmixtures have been proposed. Some have been commercially produced anddesignated as hard water soaps," allegedly free of curd formingcharacteristics when used in hard watera However, according to myinvestigations and experience, products prepared in accordance withprior art practices, even those which contain more synthetic detergentthan soap, frequently form objectionable curd in hard water under normalconditions of use. As the proportion of synthetic detergent increases,the trouble with such hard water curd may decrease in seriousness, butat the same time the cost .of the product increases and some of thedesirable physical properties found in soap are adversely affected.

As more fully hereinafter described, I have discovered that highermolecular alcohols (although possessing no power to inhibit curdformation. when used with soap alone) have a marked power to inhibitlime soap precipitation and curd formation in the case of curd-formingdetergent compositions comprising essentially a mixture of soap andsynthetic detergent in proportions more fully hereinafter described.This power exists even when the compositions are used under conditionswherein the solution is subjected to prolonged standing or to mild orvigorous agitation.

I am aware that prior workers in the art have suggested the combinationof soap with synthetic detergents (Patents 1,906A8, 2,026,816 and2,088,308). I am also familiar with recently issued patents covering theuse of certain higher alcohols with synthetic detergents to improve thesudsing and detergent power thereof (Patents 2,166,314 and 2,166,315).None of these patents, however, suggests the use of higher alcohols forinhibiting the curd formation when compositions comprising soap andsynthetic detergent are employed in hard water.

Higher molecular alcohols which come within the scope of the inventionare primary and secondary saturated or unsaturated aliphatic alcoholshaving from about 10 to about 20 carbons. Of especial interest arestraight chain primary saturated aliphatic alcohols having 10 to 14carbon atoms.

Some specific alcohols which may be used in the practice of the presentinvention are:

n-decyl alcohol, CH3 CH2 aCHaOI-I n-dodecyl alcohol, CHa(CH2) mCHaOEn-tetradecyl alcohol, CHa(CH2)12CH2OE n-hexadecyl alcohol,CHa(CH2)14CH2OH n-octadecyl alcohol, CHa(CHz)1aCHzOI-I octadecenylalcohol,

CHflCI'I?) 1CH:CH(CH:)1CH2OH Corresponding secondary alcohols such assecondary lauryl alcohol, secondary tetradecyl alcohol and the like maybe used.

Instead of employing individual alcohols as above indicated, mixtures ofsuch alcohols, especially those mixtures obtainable by reduction ofoils, fats, and waxes of animal and vegetable origin, may be employedwithout departing from the spirit of the invention. For example, themixture or higher alcohols derived by reduction of oils of the coconutoil group (a group of tropical nut oils characterized by their highcontent of lauric and myristic acids) such as coconut oil, palm kerneloil, and babassu oil are of particular value, but higher alcoholsderived by reduction of other oils and fats such as palm oil, tallow,cottonseed oil, sunflower seed oil, fish oils such as menhaden oil andthe like, as well as hydrogenated and partially hydrogenated fats andoils in general, may also be employed. In addition, higher alcoholsderived by the oxidation of aliphatic hydrocarbons, for example thosesecondary alcohols having from to carbon atoms derived by the oxidationof parailln hydrocarbons, have been found suitable in the practice ofthe invention.

The kind of soap which is used in preparing my improved detergentcompositions is not a limitation of the invention. Any of thewater-soluble soaps formulated for industrial, household, and toilet usemay be employed. Thus the character of the soap constituent may varywidely in its composition depending on whether the final ternarycomposition is to be in powdered, spray dried, flake, bar, paste,thread, liquid or other form, and it is to be understood that thespecific soaps referred to in the examples given below are not to beconstrued as limiting in nature. Water-soluble soaps such as the sodium,potassium and other suitable alkali metal or ammonium soaps or soapsprepared from nitrogen bases, such as triethanolamine, derived fromother fats and oils such as cottonseed oil, soybean oil, corn oil, oliveoil, palm oil, peanut oil, palm kernel, lard, greases, fish oils and thelike as well as their hydrogenated derivatives, and mixtures thereof,properly blended to yield the desired soap quality, may be used incompounding the ternary mixtures herein contemplated.

The synthetic detergent constituent of the present detergentcompositions may be broadly designated as a detergent of the classconsisting of water-soluble salts of organic sulfonic acids andwater-soluble salts of aliphatic sulfuric acid esters, that is,water-soluble salts of organic sulfuric reaction products having in themolecular structure a radical selected from the group consisting ofsulfonic acid and sulfuric acid ester radicals. As indicated above inthe designation of the soaps which may be used in compounding thecompositions of my invention, the choice of synthetic detergent willdepend inter alia on the physical characteristics of the final product,that is, whether the composition is to be in flake, bar, paste, or otherform. Obviously if a detergent composition in bar form is desired, itwill be impractical to combine ingredients which are too soft to retaintheir shaped form in use.

Synthetic detergents 01. special interest and particular value are thewater-soluble salts of higher alkyl sulfuric acids containing from 8 to18 carbon atoms in the alkyl radical. More specifically, the alkalimetal salts of sulfuric acid esters of normal primary aliphatic alcoholshaving 10 to 18 carbon atoms, particularly those whose principal activeingredient is a watersoluble salt of lauryl sulfuric acid or oleylsulfuric acid, have proved of value in compounding products of thepresent invention. Thus the sodium salt of alkyl sulfates obtained fromthe mixed higher alcohols derived by the reduction of coconut oil, palmkernel oil, babassu oil, or other oils of the coconut oil group or thesodium alkyl sulfate derived from sperm oil alcohols may be employed. Inaddition, water-soluble alkyl sulfates having pronounced detergent powerand derived from high molecular branched chain primary alcohols or fromhigh molecular secondary alcohols may be used.

Other aliphatic sulfuric acid esters which may be employed in thepreparation of detergent compositions of the present invention includewatersoluble salts of sulfuric acid esters of polyhydric alcoholsincompletely esterifled with high molecular weight soap formingcarboxylic acids. Such synthetic detergents include the watersolublesalts of sulfuric acid esters of higher molecular weight fatty acidmonoglycerides such as sodium salt of the coconut oil fatty acidmono-ester of l,2-dihydroxypropane-3-sulfuric acid ester,triethanolamine salt of monooleoyl diethylene glycol sulfate, sodiummono-myristoyl ethylene glycol sulfate, and sodium monolauroyldiglycerol sulfate.

Similarly water-soluble salts of ethers of high molecular weight normalprimary alcohols and lower molecular weight hydroxy alkyl sulfuric acidesters may be employed. Specific examples of such. synthetic detergentsare sodium salt of mono fatty-alcohol-of-coconut-oil ether of glycerolmonosulfuric acid and sodium salt of lauryl ether of ethylene glycolmonosulfuric acid and sodium salt of lauryl ether of diethylene glycolmonosulfuric acid.

In addition, sulfuric acid ester synthetic detergents such aswater-soluble salts of sulfated higher fatty acid alkylolamides, forexample the sodium salt of sulfated coconut oil fatty acid e'thanolamideand of sulfated babassu oilfatty acid glycerol amide, may be employed inthe practice of the invention.

The higher alcohols hereinabove mentioned are active also in inhibitingcurd formation in the case of those detergent compositions which containin combination with soap an organic synthetic detergent having a truesulfonate group. These synthetic detergents include salts of highermolecular weight monofatty acid esters of lower molecular weight hydroxyalkyl sulfonic acids such as the sodium salt of the coconut oil fattyacid monoester of 1,2-dihyroxy-propane-3-sulfonic acid, and the oleicacid ester of the sodium salt of isethionic acid. Included also are thehigher molecular weight fatty acid amides of lower molecular weightanimo alkyl sulfonic acids (for example, potassium salt of oleic acidamide of N-methyl taurine), the water-soluble salts of the highermolecular weight alcohol esters of sulfocarboxylic acids (for example,sodium salt of the lauryl alcohol ester of sulfoacetic acid), lowermolecular weight sulfocarboxylic acid amides of alkylolamine esters ofhigher molecular weight fatty acids (for example, sodium salt of thesulfoacetamide of amino ethyl laurate), higher alkylated aryl sulfonicacids (for example, potassium salt of the sulfonic acid derived from thecondensation product of benzene and a chlorinated kerosene fractioncontaining predominantly 12 carbon atoms per molecule), and ethers ofhigher molecular weight alcohols and lower molecular weight hydroxyalkyl sul- Ionic acids(for example, monolauryl ether of the sodium saltof isethionic acid).

Although the cleansing agent of the compositions of the presentinvention comprises essentially a ternary mixture of higher alcohol,soap and synthetic detergent, it will be appreciated that theincorporation in the mixture of additional ingredients commonly usedwith cleansing compositions, such as perfumes, starch, urea,triethanolamine, inorganic salts (silicates, carbonates, ortho-, meta-,pyro-, and triphosphates and the like), albuminous substances, glycerin,insecticides and germicides and the like, is contemplated as part of theinstant invention.

The following examples will illustrate the manner in which the inventionmay be practiced, but it is to be understood that such details are givenmerely for exempliflcation purposes and are not to be construed aslimiting the scope of the appended claims. In all instances theproportions are expressed in parts by weight.

Example 1.Five parts of an unfractionated mixture of higher molecularalcohols derived by the reduction of coconut oil, 70 parts of sodiumsoap derived from a mixture of 80% tallow and coconut oil and containingabout 15% moisture, and parts of a commercial alkyl sulfate containingabout 88% synthetic detergent (the sodium salt of alkyl sulfuric acidsderived from coconut oil alcohols) were mixed and milled by passing oversoap milling rolls in accordance with accepted procedure to produce ahomogeneous product. The product resulting from the milling was thenplodded and cut and stamped in the form of a bar. The ratio ofsoapzsynthetic was about 27:1, and the ratio of syntheticzalcohol wasabout 4.421. The detergent bar may be employed with 21 grain hard waterin the washstand or bathtub for toilet use without the formation ofobjectionable soap ring.

In an ancillary example, lauryl alcohol or myristyl alcohol instead ofthe mixture of alcohols derived from coconut oil may be used.

. Example 2.-In accordance with the procedure of Example 1 a detergentbar was prepared from the same three ingredients with amounts asfollows: l6 parts-coconut oil higher alcohol, 24 parts alkylsulfatesynthetic detergent, parts soap. The ratio of soapzsynthetic was about24:1, and the ratio of syntheticzalcohol was about 1.3:1.

Instead of employing coconut oil alcohol as set forth in Example 2, amixture of C10 to C20 secondary alcohols derived by the oxidation ofparaffin wax may be used.

Another example along the same lines involves substitution of 26.4 partsof Nacconol NRSF (a synthetic detergent product containing 80% of thesodium salt of the sulfonic acid of the condensation product of benzeneand the chloride of a kerosene fraction containing predominantly 12carbon atoms, in the hydrocarbon chain, and 20% inorganic salts) for the24 parts alkyl sulfate used in Example 2.

Example 3.In accordance with the procedure of Example 1, a detergent barwas prepared from the same three ingredients with amounts asfolsubstitution of about 255 parts of the sodium salt of the sulfuricacid mono-ester of coconut oil monoglyceride or of about 55.5 parts of"Igepon A" (containing 46% ot the oleic acid ester of sodium isethionateas the active synthetic de- 1 tergent and about 54% of inorganic salts)for the alkyl sulfate synthetic detergent used in Example 3.

Example, 4.The following mixture was suitably milled and converted intobar form. 15 parts octadecyl alcohol, 60 parts of the same soap used inExample 1, and 25 parts of Nacconol LA" (containing about 73% of thesodium salt of coconut 011 higher alcohol ester of sulfoacetic acid asthe active synthetic detergent and about 27% inorganic salts). The ratioof soap:synthetic was about 2.8:1, and the ratio of syntheticzalcoholwas-about 12:1. The product was used in 21 grain hard water without theformation of objectionablesticky curd.

An efllcient bar may also be produced by substituting about 18.2 partsof sodium oleyl sulfate or of coconut oil monoglyceride sodium sulfonatefor the 25 parts of "Nacconol LA" used in Example 4.

Example 5.-5l.6 parts of dry sodium soap prepared from fish oilhydrogenated to an iodine value of about 65, 16.1 parts of dry sodiumsoap prepared from coconut oil, 24.3 parts of alkyl sulfate detergentused in Example 1, and 8 parts of an unfractionated mixture of highermolecular alcohols derived by the reduction of coconut oil were combinedand mixed with about 4% water. The mixture was then run over a soapmilling roll until a homogeneous mixture of ingredients was obtained.The soap was removed from the rolls in the form of thin ribbons whichwere dried and then broken up into suitable flake form. In thecomposition thus prepared, the ratio of soaprsynthetic was about 3.221,and the ratio of syntheticzalcohol was about 2.7 :1. No sticky curd isformed when the flakes are used to wash dishes in water of 21 grainhardness.

In an ancillary example, 21.4 parts of the oleic acid amide of thesodium salt of methyl taurine may be substituted for the alkyl sulfatesynthetic detergent used in Example 5.

Example 6.32 parts dry sodium soap derived from tallow, 8 parts of drypotassium soap from coconut oil, 48.4 parts of the sodium salt of laurylether of ethylene glycol monosulfuric acid, and 5 parts; of decylalcohol are mixed with about 4 parts water and milled and converted intoflake form as in Example 5. In'the instant example the ratio of soap:synthetic is about 0.83:1 and the ratio of syntheticzalcohol is about9.7:1.

Other examples along the same line involve the substitution of thesodium salt of sulfated coconut oil fatty acid ethanolamide, or thesodium salt of the sulfo acid amide of amino ethyl laurate, or themonolauryl ether of 1,2-dihydroxy-propane-S-sodium sulfonate, for thesynthetic detergent used in Example 6.

Example 7 .3 .parts of mixed alcohols derive by the reduction of coconutoil are mixed with 81 parts of essentially dry sodium soap derived froma mixture of 75% tallow and 25% coconut oil; and with 16 parts of thedry sodium salt of the sulfuric acid esters of coconut oilmonoglyceride. Enough water is added to produce a homogeneous coherentflake when the mixture is subsequently passed over soap milling rolls toconvert it into flake form. In the mixture thus formed the ratio ofsoapzsynthetic is 51:1, and the ratio of syntheticzalcohol is 5.3:1. Theresulting product may be used for detergent purposes in hard water withdecreased formation of hard water curd.

Example 8.23 parts of mixed alcohols used in Example 7 are mixed with 54parts of sodium soap used in Example 7, and with 23 parts .of the drysodium salt of the sulfonic acid of the condensation product of benzeneand the chloride of a kerosene fraction containing predominantly 12carbon atoms. Enough water is added to give a homogeneous paste uponstirring at elevated temperature. The ratio of soap:synthetic is about2.4:1, and the ratio of syntheticzalcohol is about 1:1. detergentpurposes with decreased formation hard water curd.

E's-ample 9.24 parts of the mixed alcohols used in Example 'I are mixedwith 36 parts of sodium soap used in Example 7, and with 40 parts of thedry sodium salt of the sulfuric acid ester of mixed alcohols derived bythe reduction of coconut oil. Enough water is added to give ahomogeneous paste upon stirring at elevated temperature. The ratio ofsoapzsynthetic is about 0.9:1. and the ratio of synthetic:alcohol isabout 1.7:1.

Example 10.4 parts of the mixed alcohols used in Example 7 are mixedwith 36 parts of the dry soap used in Example 7, and with 60 parts ofthe synthetic detergent used in Example 8. Enough water is added toproduce a homogeneous coherent flake when the mixture is passed over Theresulting product may be used for soap milling rolls. The ratio ofsoapzsynthetic is about 0.621, and the ratio of soapzalcohol is about15:1.

Example 11.- 10 parts of the mixed alcohols used in Example 7 are mixedwith parts of the soap used in Example 7, and with 40 parts of thesynthetic detergent used in Example 9. Enough water is added to producea homogeneous coherent flake when the mixture is passed over soapmilling rolls. The ratio of soap:synthetic is about 1.221, and the ratioof synthetic:alcohol is about 4: 1.

Reference has been made above to the use of the detergent compositionsof the present invention in water of 21 grains of hardness per gallon.It is to be understood, however, that 21 grain water is referred to onlyas being representative of hard waters in general. According to myexperience and investigations my ternary detergent composition iseifective in hard water of any municipal water system or anydomestically used water source of which I am aware.

Besides possessing resistance to curd formation in hard water, productsof the present invention dissolve at a desirable rate in water, sudsprofusely and cleanse emciently. I

The amount of alcohol that can advantageously be used decreases withincreasing molecular weight of the alcohol and is also to a degreedependent upon the nature and amount of synthetic detergent present inthe composition, but it has been found that the most useful productsresult when the amount of alcohol exceeds 5 per cent of, but is notgreater than. the amount of synthetic detergent present and constitutesat least 2 per cent of the combined weights of the soap, synthetic andalcohol.

In connection with the use of synthetic detergents made from higheralcohols, such as the alhrl sulfates for example, the desired proportionof alcohol in the final mixture may be arrived at by employing asynthetic which has been prepared .under controlled conditions ofreaction adapted to leave unreacted higher alcohol in the product inuitable proportion.

Most of the above examples cover compositions in which theratios ofessential ingredients come within the preferred ranges, that is, a ratioof soapzsynthetic from about 0.6:1 to about 4:1 and a ratio of synthetic:higher alcohol from about 1:1 to about 10:1. The advantages of mydiscovery, however, are to be realized in compositions falling outsidethe preferred ranges of proportions, and accordingly compositions comingwithin the ratios of soap:synthetic of about 0.5:1 to about 6:1 and ofsyntheticzhigher alcohol 0! about 1:1 to about 20:1 are contemplated aspart of the broad invention, the higher alcohol constituting at least 2per cent of the combined weights of soap, synthetic, and higher alcohol.Optimum results in the case of each composition may be realized byadjustment of the ratios used depending on the types of soap, syntheticdetergent, and higher alcohol employed.

As indicated above, the physical form of the compositions is not alimitation of the invention and may be varied in well known manner. Insome instances, however, it may be necessary to adjust temperatureconditions or moisture content of the mixture to give a product of thedesired consistency for handling in the various processing operationsrequired in the development of the desired physical form. Suchadjustments of course are well within the scope of those skilled in theart.

. The manner of mixing the ingredients is not a limitation of theinvention. Any suitable mixing device such as a series of milling rollsordinarily used in mixing plastic soap with added incredients 0rcrutching mechanism of high mixing efficiency as employed in mixing morefluid constituents may be employed to effect homogeneity in the mixtureof higher alcohol, soap, and synthetic detergent.

Having thus described myinvention, what I claim and desire to secure byLetters Patent is:

-1. A detergent composition characterized by reduced tendency to formsticky lime curd when used in hard water at rinsing dilutions,comprising essentially a ternary mixture of a watersoluble soap, awater-soluble salt 01' an organic sulfuric reaction product havingpronounced detergent properties and having in it molecular Isoap:sulfuric reaction product salt being from about 0.5:1 to about 6:1,the ratio of sulfuric reaction product saltzhigher alcohol being fromabout 1 :1 to about 20:1, and the amount of higher alcohol constitutingat least 2 per cent of the combined weights of the soap. sulfuricreaction product salt and higher alcohol.

2. A detergent composition characterized by reduced tendency to formsticky lime curd when used in hard water at'rinsing dilutions,comprising essentially a ternary mixture of a water-soluble soap, awater-soluble salt of an organic sulfuric reaction product havingpronounced detergent properties and having in its molecular structure aradical selected from the group consisting of sulfonic acid and sulfuricacid ester radicals, and a higher aliphatic alcohol selected from thegroup consisting of primary and secondary saturated and unsaturatedhigher alcohols having from to carbon atoms, the ratio of soap:suliuricreaction product salt being from about 0.6: 1 to about 4:1, the ratio ofsulfuric reaction product saltzhigher alcohol being from about 1:1 toabout 10:1, and the amount of higher alcohol constituting at least 2 percent of the combined weights of the soap, sulfuric reaction product saltand higher alcohol.

3. The composition of claim 1 in which the higher alcohol is a mixtureof higher molecular primary alcohols obtainable by reduction of anaturally occurring fat.

4. The composition of claim 1 in which the higher alcohol is a mixtureof higher molecular primary alcohols derived from an oil of the groupconsisting of coconut, palm kernel and babassu oils and consistingpredominantly of saturated alcohols having 10 to 14 carbon atoms.

5. The composition of claim 1 in which the higher alcohol is a mixtureof higher molecular primar alcohols derived from coconut oil andconsisting predominantly of saturated alcohols having 10 to 14 carbonatoms.

6. The composition of claim 1 in which the higher alcohol consistspredominantly of lauryl alcohol.

7. The composition of claim 1 in which the higher alcohol consistspredominantly of decyl alcohol.

8. The composition of claim 1 in which the higher alcohol consistspredominantly of tetradecyl alcohol.

9. The composition of claim 1 in which the organic sulfuric reactionproduct salt is a watersoluble salt of an alkyl sulfuric acid havingfrom 10 to 18 carbon atoms in the alkyl radical.

10. The composition of claim 1 in which the sulfuric reaction productsalt is a water-soluble salt of alkyl sulfuric acids of higher alcoholsde-' rived from an oil of the group consisting of coconut, palm kerneland babassu oils.

11. The composition of claim 1 in which the sulfuric reaction productsalt consists of a watersoluble salt of dodecyl sulfuric acid and inwhich the higher alcohol consists of lauryl alcohol.

12. The composition of claim 1 in which the sulfuric reaction productsalt consists of a watersoluble salt of a higher alkylated aryl sulfonicacid.

13. The composition of claim 1 in which the sulfuric reaction productsalt is a water-soluble salt of the coconut oil-fatty acid-monoester ofl,2-dihydroxy-propane-3-sulfuric acid ester.

14. A detergent composition characterized by reduced tendency to formsticky lime soap curd when used in hard water at rinsing dilutions,comprising essentially a mixture of a water-soluble soap, awater-soluble salt of an alkyl sulfuric acid having from 10 to 18 carbonatoms in the alkyl radical, and high molecular primary allphaticalcohols derived from an oil of the group consisting of coconut, palmkernel and babassu oils and consisting predominantly of saturated al-REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,004,874 La zier June 11, 19352,026,816 Bertsch Jan. 7, 1936 2,166,314 Martin July 18, 1939Certificate of Correction Patent No. 2,527,075 October 24, 1950 WALTERC. PRESTON It is hereby certified that error appears in the printedspecification of the above ni mbered patent requiring correction asfollows:

Column 1, line 44, for difficulty read diyfimdtly; column 7 line 42, for1.2 :1 read 1.3 :1;

. and that the said Letters Patent should be read as corrected above, sothat the same may conform to the record of the case in the PatentOflice. Signed and sealed this 2nd day of January, A. D. 1951.

THOMAS F. MURPHY,

Assistant Oommiaaioner of Patents.

1. A DETERGENT COMPOSITION CHARACTERIZED BY REDUCED TENDENCY TO FORMSTICKY LIME CURD WHEN USED IN HARD WATER AT RINSING DILUTIONS,COMPRISING ESSENTIALLY A TERNARY MIXTURE OF A WATERSOLUBLE SOAP, AWATER-SOLUBLE SALT OF AN ORGANIC SULFURIC REACTION PRODUCT HAVINGPRONOUNCED DETERGENT PROPERTIES AND HAVING IN ITS MOLECULAR STRUCTURE ARADICAL SELECTED FROM THE GROUP CONSISTING OF SULFONIC ACID AND SULFURICACID ESTER RADICALS, AND A HIGHER ALIPHATIC ALCOHOL SELECTED FROM THEGROUP CONSISTING OF PRIMARY AND SECONDARY SATURATED AND UNSATURATEDHIGHER ALCOHOLS HAVING FROM 10 TO 20 CARBON ATOMS, THE RATIO OF SOAP:SULFURIC REACTION PRODUCT SALT BEING FROM ABOUT 0.5:1 TO ABOUT 6:1, THERATIO OF SULFURIC REACTION PRODUCT SALT: HIGHER ALCOHOL BEING FROM ABOUT1:1 TO ABOUT 20:1, AND THE AMOUNT OF HIGHER ALCOHOL CONSTITUTING ATLEAST 2 PER CENT OF THE COMBINED WEIGHTS OF THE SOAP, SULFURIC REACTIONPRODUCT SALT AND HIGHER ALCOHOL.